KR20170063696A - Method for producing an organic electronic component, and organic electronic component - Google Patents

Abstract

상기 구조식에서, E¹과 E²는 서로 독립적으로 산소, 황, 셀레늄, NH 또는 NR'일 수 있고, 여기서 R'은 알킬 또는 아릴을 포함하는 군으로부터 선택되고 리간드 L의 치환된 벤젠환과 결합될 수 있으며; 치환기 R¹은 서로 독립적으로 1 내지 10개의 C 원자를 갖는 분지형 또는 비분지형 플루오르화 지방족 탄화수소를 포함하는 군으로부터 선택되고, 여기서 n은 1 내지 5이고; 치환기 R²는 서로 독립적으로 -CN, 1 내지 10개의 C 원자를 갖는 분지형 또는 비분지형 지방족 탄화수소, 아릴 및 헤테로아릴을 포함하는 군으로부터 선택되고, 여기서 m은 0 내지 최대 5-n이다. The present invention relates to a method of manufacturing an organic electronic device, the device comprising at least one organic electronic layer having a matrix, the matrix comprising a metal complex as a dopant, the metal complex comprising at least one metal atom M and a metal atom M, wherein the ligands L independently of one another have the following structure: the dopant of at least one organic electronic layer is deposited by vapor deposition using an evaporation source, and the deposition source Wherein the dopant is configured to collide with at least one wall of the evaporation source.

In this structure, E ¹ and E ² can be, independently of one another, oxygen, sulfur, selenium, NH or NR ', wherein R' is selected from the group comprising alkyl or aryl and is bonded to a substituted benzene ring of ligand L ; The substituent R &^lt; 1 > is independently selected from the group comprising branched or unbranched fluorinated aliphatic hydrocarbons having 1 to 10 C atoms, where n is 1 to 5; Substituent R ² is independently from each other selected from the group comprising -CN, a branched or unbranched aliphatic hydrocarbon having 1 to 10 C atoms, aryl and heteroaryl, wherein m is from 0 to a maximum of 5-n.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing an organic electronic device and an organic electronic device,

The present invention relates to a method for producing an organic electronic device in which an organic electronic layer is obtained by vapor deposition. The present invention also relates to an organic electronic device.

Organic electronic devices relate to the use of organic matrix materials to convert light into and out of current and to the construction of electrical devices using organic semiconductor materials. Examples of the above categories are, for example, photodetectors and organic solar cells that convert light into electrical signals or currents, as schematically shown in FIG. 1, and organic light emitting diodes capable of forming light using organic electronic materials OLED) (see Fig. 2). A field effect transistor or bipolar transistor is included in the second technical field, for example, which reduces the contact resistance between the electrode and the semiconductor material, as schematically illustrated in FIG.

All applications commonly include an electrotransport layer as an essential functional element, and the electrotransport layer comprises a different conduction mechanism depending on its composition. It is generally distinguished by the intrinsic p-type (hole) or n-type (electron) conductivity of an organic material. Because the charge transport of these organic species is generally not sufficient, the organic species are mixed with additional compounds that improve the charge transport properties of the layer. Generally this is done by doping with metallic or other organic compounds. A method for achieving a definite improvement in conductivity is the addition of a metal complex.

For example, the inventors of the present invention have already described the use of bismuth and copper complexes as p-type dopants for organic electronic devices in WO 2013/182389 A2 and WO 2011/033023 A1.

 An organic layer of the above-described elements comprising a matrix material together with a respective metal complex as the p-type dopant is obtained, for example, by a solvent process, e. g. by wet process technology. In addition, in the above-mentioned patent publication, the organic layer is also formed by vapor deposition using a point source.

Examples of wet processing techniques are in particular printing techniques such as ink jet, gravure printing and offset printing. Spin and slot coating are also common solvent processes.

The formation of layers of organic electronic devices by a vacuum process is otherwise achieved by sublimation, i.e. by thermal evaporation. Wherein the organic layer is deposited from a vapor phase on a substrate or over a conventional layer.

Currently, the most efficient organic devices are manufactured by the processes described above, and these devices are being sold by pilot production in the meantime. The efficiency of organic electronic devices is achieved, in particular, by the fact that the devices are composed of a very large number of discrete layers. Each layer has a special physical electrical function associated with its location within the device.

In the production of the organic layer by vapor deposition, the matrix material and the dopant are deposited, for example, preferably on a substrate or an existing layer by simultaneous evaporation from various deposition sources.

A point vapor source is generally used for this purpose. For example, vapor deposition of organic layers doped by the inventors of the present invention in WO 2011/033023 A1 and WO 2013/182389 A2 was carried out using point vapor sources, respectively.

During deposition from a point vapor source, the deposited material evaporates in a vacuum crucible. After evaporation of the material, the molecules reach the substrate without collision due to the high mean free path in vacuum (10 ^-5 to 10 mbar ^-6 ). That is, in order to be able to deposit on the substrate without decomposition, the material must be thermally stable even if the sublimation temperature is slightly exceeded.

Two technologies, wet process technology and vapor deposition by vapor deposition sources are relatively safe technologies. Thus, the techniques described above can be used for a number of different metal complexes.

Although vapor deposition and wet process techniques using point vapor sources make it possible to produce organic electronic devices even under industrial conditions, the techniques described above are particularly suited only to the coating of large area substrates.

It is an object of the present invention to provide another method for producing an organic electronic device, particularly a method suitable for coating a large area substrate.

This problem is solved by the method according to claim 1.

Accordingly, a method of manufacturing an organic electronic device is proposed, and the device includes one or more organic electronic layers. The organic electronic layer also includes a matrix, which comprises a metal complex as a dopant. For example, the above-described dopant may be a p-type dopant. Said metal complex comprises at least one ligand L bonded to at least one metal atom M and a metal atom M, wherein the ligands L independently of one another have the general structure:

Wherein E ¹ and E ² are independently of each other oxygen, sulfur, selenium, NH or NR ', wherein R' may be selected from the group comprising alkyl or aryl and is bonded to the substituted benzene ring of ligand L .

The substituent R &^lt; 1 > is independently selected from the group comprising branched or unbranched fluorinated aliphatic hydrocarbons having 1 to 10 C atoms, where n is 1 to 5. That is, for example, there can be from 1 to 5 substituents R ¹ , each of which may be selected independently from the group consisting of branched or unbranched fluorinated aliphatic hydrocarbons each having 1 to 10 C atoms It is possible. Thus, for example, a plurality of the same and a plurality of different substituents R ¹ may be present.

Substituent R ² is independently from each other selected from the group comprising -CN, branched or unbranched aliphatic hydrocarbons having 1 to 10 C atoms, aryl and heteroaryl, wherein m is from 0 to a maximum of 5-n. Thus, for example, there is at least one substituent R < ^{2 &} gt ;, wherein the substituents are independently of each other selected from the group consisting of -CN, a branched or unbranched aliphatic hydrocarbon having 1 to 10 C atoms, aryl and heteroaryl It is possible to be selected. However, for example, it is also possible that the ligand L does not include the substituent R < ^{2 &} gt ;.

The ligand L comprises always at least one substituent R < ^{1 &} gt ;, but not necessarily the substituent R < ^{2 &} gt ;.

All unsubstituted positions of the benzene ring of the ligand L are occupied by hydrogen or deuterium.

The metal M can be, for example, a rare earth metal or a transition metal.

Deposition of a dopant of one or more organic electronic layers is performed by an evaporation source for vapor deposition, wherein the evaporation source is configured such that the dopant impinges on at least one wall of the evaporation source.

Unlike the evaporation source used in the present invention, in the case of the point vapor source, since the area of the evaporation source where the dopant is evaporated, the discharge opening of the evaporation source, and the substrate on which the dopant is deposited are all arranged in a straight line, And collision with the wall of the evaporation source can be prevented.

In the case of the evaporation source used in the method according to the present invention, the area of the evaporation source where the dopant is evaporated, the discharge opening of the evaporation source and the substrate are not arranged in a straight line. The deposition source is rather characterized in that the dopant is further deflected in the evaporation source before the dopant reaches the substrate after leaving the evaporation source after the dopant has evaporated in the region of the evaporation source.

For example, the dopant collides with a plurality of walls of the evaporation source. For example, a gas stream containing a dopant can be guided over the area of the evaporation source in approximately tubular form, where the dopant collides with the walls of the evaporation source many times. For example, the walls of the evaporation source can be heated, so that the wall has a temperature at least as high as the sublimation temperature of the dopant.

Such evaporation sources provide the advantage of enabling improved guidance of the gas flow, unlike conventional evaporation sources for vapor deposition. This may be particularly desirable for vapor deposition on substrates with a large area to be coated.

In the method according to the invention, for example, the dopant can collide with the walls of the evaporation source thousands of times without decomposition, before the dopant leaves the evaporation source.

The dopant deposited in many evaporation sources undergoes thousands of collisions with the walls of the evaporation source, for example until it enters the free vacuum through a gap or a plurality of hole-shaped discharge openings. To prevent material deposition on the walls of the evaporation source, the walls are typically heated to a temperature higher or 20 to 80 K (Kelvin) above the actual sublimation point of the deposited dopant. The dopant can withstand this temperature when vapor-deposited, and is not decomposed.

The inventors of the present invention have found that conventional metal complexes which are used as dopants in the organic layer and which are sufficiently stable for treatment by, for example, wet process techniques or vapor deposition using a point vapor source can be deposited using an evaporation source , Where the dopant collides with at least one wall of the evaporation source.

For example, the inventors of the present invention have found that the p-type dopants of WO 2013/182389 A2 and WO 2011/033023 A1 are deposited by a solvent process and by vapor deposition from a point vapor source, in the form of an organic layer with a suitable matrix material , Many of the compounds mentioned in the publication have found that the dopant is not sufficiently temperature stable for deposition by an evaporation source that impacts the walls of the evaporation source. For example, the inventors of the present invention have found that, for example, metal complexes of copper or bismuth are not sufficiently stable for deposition when they do not contain substituents of the R < ^{1 >} form. For example, benzoic acid derivatives containing a fluorinated benzene ring but not including a substituent in the R < ^{1 >} form are not sufficiently stable for use in the process according to the present invention.

The inventors of the present invention have found that the metal complexes used in the process according to the invention according to claim 1 have surprisingly sufficient thermal stability that they can be evaporated and deposited by means of an evaporation source, And to collide with at least one wall of the circle.

That is the inventor in particular, may be a certain improvement of the thermal stability of the whole complex achieved by a branched or unbranched fluorinated introduction of the aliphatic hydrocarbon group of R ^1, at least one substituent having 1 to 10 C atoms, whereby the claim It was found that deposition by the evaporation source according to item 1 was only possible.

At the same time, the metal complexes used in the process according to the invention are characterized by a high enough temperature stability as well as a sufficiently good doping concentration.

The layer of the organic electronic device formed by the method according to the invention is also characterized by high optical transparency in the visible range.

The metal complexes used in the process according to the invention can be purchased at similar prices as conventional metal complexes and can be manufactured without great technical complexity.

The use of an evaporation source in which the dopant impinges on at least one wall of the evaporation source also allows for such an inexpensive and time-saving, inexpensive manufacture of organic electronic components. Thus, the method according to the invention is particularly suitable for application in industrial standards. The method according to the present invention is even more suitable than the conventional method, for example, using a point vapor source, in particular for coating large area substrates. In short, the method according to the present invention is a large-area coating method.

Hereinafter, some definitions of terms are briefly mentioned:

The term "organic electronic device" in the context of the present invention generally means and / or includes, in particular, organic transistors, organic light emitting diodes, luminescent electrochemical cells, organic solar cells, photodiodes and organic photovoltaic cells.

The term "p-type dopant " in the context of the present invention encompasses or implies a material which has, in particular, a Lewis acidity and / or is capable of forming a complex comprising a matrix material, Lewis < / RTI > azide. ≪ / RTI >

In the following, a series of preferred embodiments of the method according to the invention are described:

According to a particularly preferred embodiment, in the method according to the present invention, a linear evaporation source is used for vapor deposition.

In the linear evaporation source, vapor deposition is performed through a gap as a discharge opening in the form of a row of holes. Here, the molecules often undergo thousands of collisions with the walls of most of the evaporation sources, usually until they enter the free vacuum only through a gap or a number of holes. In order to prevent material deposition on the walls of the linear evaporation source, the linear evaporation source is heated to a temperature 20 to 80 K above the actual sublimation point. It is also possible to heat to a higher temperature.

 Conventional dopants are mostly decomposed when colliding with the walls of the evaporation source. For example, the inventors have found that most of the metal complexes of WO 2013/182389 A2 and WO 2011/033023 Al are sufficiently stable for deposition using a point vapor source, but as the experiment proved, the complex collides with the walls of the evaporation source Which is deposited by a linear evaporation source.

The compounds described in Schmid et al. [Fluorinated Copper (I) Carboxylates as Advanced Tunable p-Dopants for Organic Light-Emitting Diodes "(Advanced Materials 2014, 26th Edition, 6, 878-885) are also p-type dopants. The compounds described therein by the inventors of the present invention could be deposited and characterized in a point vapor source without decomposition, but migration to a linear vapor source was not possible.

According to a preferred embodiment, in the process according to the invention, a metal complex of the abovementioned type which is a Lewis acid is used, i.e. the metal complex acts as an electron pair acceptor. This has been found to be particularly desirable for interaction with the matrix material.

An embodiment of the present invention relates to a method according to the invention wherein the metal complex has the same number of ligands L. These complexes can be prepared much more simply than metal complexes with different ligands L.

An embodiment of the present invention relates to a method according to the invention wherein the metal complex comprises at least two different ligands L. These complexes can also be deposited in an evaporation source configured to cause the dopant to collide with at least one wall of the evaporation source.

An embodiment of the present invention relates to a method according to the invention wherein the metal complexes further comprise ligands other than L and other ligands of a different formula. These complexes are also characterized by high thermal stability.

According to another refinement of the invention, a metal complex with at least one open or partially accessible coordination site is used in the process according to the invention. It has also been found to be particularly desirable for interaction with matrix materials.

A preferred embodiment of the present invention relates to a process according to the invention, wherein the metal M of the metal complex is selected from the group consisting of a rare earth metal and a transition metal. In particular, the metal M may be a rare earth metal and metal Cu, Cr, Mo, Rh and Ru of Groups 13 to 15 of the periodic table.

These complexes have been effectively used as p-type dopants in the organic layer of organic electronic devices. Excellent p-type dopant effects are achieved with the complexes of metals described above according to the Lewis acidity of the dopant. In addition, the above-described metal complexes can be simply produced and do not require complicated manufacturing methods. The conductivity of the organic layer can also be adjusted to the relevant requirements simply by the concentration of the dopant of the metal mentioned above.

Another improvement of the present invention relates to a method according to the invention, wherein the metal M of the metal complex is bismuth or copper. For example, a metal complex comprising bismuth in the oxidation state III or V. Further, a bismuth complex in the oxidation state III is particularly preferable. For example, the metal complex may be a copper (I) or copper (II) complex. Copper complexes in oxidation state I are also particularly preferred.

Metal complexes of copper and bismuth have been effectively used as particularly efficient p-type dopants which can be produced simply. For example, organic electronic devices comprising a hole transport layer having the dopants described above are characterized by particularly good conductivity. In addition, the corresponding complexes are particularly thermally stable.

In a particularly preferred embodiment, the substituent R < ¹ > is at least a double fluorinated substituent, i.e., R < ¹ > comprises at least two fluorine atoms. It is more preferable that the substituent R ¹ is a perfluorinated substituent. The higher the degree of fluorination, the greater the effect of stabilizing the substituent on the metal complex.

A particularly preferred embodiment of the invention relates to a process according to the invention wherein at least one substituent R ¹ of the ligand L in the metal complex is a -CF ₃ group.

The inventors of the present invention have found that the process according to the present invention comprising a metal complex of the above kind has the advantage that such a metal complex has a particularly high thermal stability and therefore can be used in an evaporation source in which the metal complex collides with at least one wall of the evaporation source It was found that it is preferable since it is not decomposed even when it is used.

The inventors have found that the electronic and stereochemical properties of the -CF ₃ group as a substituent R ¹ of ligand L lead to particularly stable metal complexes. In particular, very high thermal stability becomes possible, so that metal complexes containing -CF ₃ groups as substituents R ¹ of ligand L are decomposed only at temperatures much higher than the sublimation point.

In addition, the -CF ₃ group promotes the higher Lewis acidity of the metal complex and in particular leads to an excellent dopant concentration, which promotes conductivity in the organic layer of the prepared organic electronic device.

Also, because ligands containing -CF ₃ substituents diffuse widely in the starting material for the preparation of ligands L, unlike other fluorinated aliphatic hydrocarbons, the ligands in which the substituent R ¹ is a -CF ₃ group are more likely to be ligands than the ligands containing other substituents R ¹ It is easier to access and cheaper.

Another aspect of the invention relates to a method according to the invention, wherein the ligand L and contains exactly two substituents R ^1, the substituent forms a group -CF _3, respectively.

The inventors of the present invention, surprisingly, for example, was identified that further improvement of the second temperature stability of the metal complex by the use of a group of -CF _3, as opposed to using a single -CF _3-deception may be achieved. This results in particularly good results in the case of stacking the organic layer containing the metal complex as a dopant by using an evaporation source in which a collision of at least one wall of the evaporation source with a dopant, that is, a dopant, occurs.

Another embodiment of the present invention is directed to a method according to the present invention, wherein the ligand L contains exactly two substituents R ^1, and said substituents are each optionally substituted in the benzene ring of the group -CF ₃ form, and ligand L 3,5 - position.

The inventors of the present invention have found that a complex comprising ligand L of the above-mentioned connectivity enables a particularly high thermal stability. The inventors have found that the stereochemical requirements of the group at the 3,5-position in the benzene ring enable particularly good stabilization of the metal complex.

Another embodiment of the invention relates to a process according to the invention in which the substituents R ² are, independently of one another, -CN, methyl-, ethyl-, n-propyl-, iso-propyl-, n- Butyl-, tert-butyl-, and substituted or unsubstituted phenyl-.

The inventors of the present invention have found that the evaporation of such a complex by an evaporation source in which the dopant collides with at least one wall of the walls of the evaporation source is possible without decomposition of the complex. That is, a complex containing a ligand L can also be used in a linear evaporation source, and not all substituents in the linear evaporation source are fluorinated hydrocarbons.

Another embodiment of the present invention relates to a method according to the invention wherein the ligand L of the metal complex does not comprise a substituent R ² , i.

Since the non-fluorinated hydrocarbon substituent has a higher reactivity than the fluorinated hydrocarbon substituent, the omission of the substituent R < ² > means that there is an improved deposition potential in the vapor phase by the vapor source in which the metal complex collides with at least one wall of the vapor source source, Leading to further improvement in stability.

In another preferred refinement of the invention, the metal complex comprises exactly two substituents R < ^{1 >} or more substituents R < ^{1 &} gt ;. The two or more substituents R < ¹ > enable a particularly good blocking of the complex to the outside, thus allowing a particularly good stabilization of the metal complex.

A further refinement of the invention relates to a process according to the invention wherein E ¹ and E ² of the ligand L of the metal complex are oxygen. In this case the ligand L is a derivative of a benzoate substituted with a fluorinated hydrocarbon.

The inventors of the present invention have found that these metal complexes can be produced simply and that a metal complex with an excellent dopant concentration is formed and that it meets particularly demanding requirements for thermal stability so that at least one of the walls of the evaporation source and the dopant Have found that these metal complexes are particularly suitable for the production of organic electronic devices using vapor deposition by a colliding vapor source. In particular, derivatives of benzoic acid are often commercially available or can be made without high technical complexity.

A particularly preferred embodiment of the invention relates to a process according to the invention wherein the ligands L of the metal complex are, independently of one another,

≪ / RTI >

When there are a plurality of ligands L, all the ligands L of the metal complex can be selected independently of each other. For example, there may be a number of different ligands L as described above in the metal complex, or all ligands L may be the same.

The inventors of the present invention have found that a metal complex containing the ligand L of the above group has particularly excellent heat resistance and also has particularly excellent dopant characteristics. Surprisingly, it has been found that the metal complex is particularly suitable for deposition by an evaporation source in which the metal complex collides with at least one wall of the evaporation source but is not decomposed in the evaporation source.

Another preferred embodiment of the present invention relates to a process according to the invention wherein the ligands L of the metal complex are, independently of one another,

≪ / RTI >

The above-described examples of the ligand L are commercially available at a reasonable price and therefore do not have to be produced in-house. Therefore, the above examples are particularly suitable for application in industrial standards.

Another preferred embodiment of the present invention relates to a process according to the invention wherein the ligand L of the metal complex is

이다.

to be.

By using a benzoic acid derivative containing two -CF ₃ substituent groups at the 3,5-position, a metal complex having thermal stability even when the sublimation temperature is far exceeded can be obtained. Such complexes are particularly suitable for methods involving deposition by an evaporation source, such as a linear evaporation source, which collides with at least one of the walls of the evaporation source. Further, an organic electronic device having excellent electrical characteristics is formed.

In another embodiment of the process according to the invention, the metal complex used is a mononuclear metal complex, i.e. a metal complex with only one central atom.

Polynuclear metal complexes are used in yet another embodiment of the process according to the invention. This makes it possible to better control the conductivity of the organic layer to be deposited mainly by the availability of a plurality of Lewis acid sites.

Another embodiment of the invention relates to a process according to the invention in which only homoleptic metal complexes are used. Such complexes can usually be prepared so uncomplicated because the complexes contain only ligands similar to the ligand L's formula. Other ligands that can potentially reduce the stability of the overall complex can therefore not be introduced.

Another embodiment of the present invention relates to a method according to the present invention wherein ligand L is bound to metal atom M independently of each other by one of the following types of coordination:

The inventor's experimental discovery demonstrates that the bond to the metal atom M can vary. To achieve increased temperature stability, the ligand can be in one position, in two positions, or in cross-linkage.

A particularly preferred embodiment of the present invention relates to a process according to the invention wherein the metal complex is a bismuth complex and the ligands L may independently of one another have the general structure:

Wherein the substituent R &^lt; 1 > is selected from the group comprising branched or unbranched fluorinated aliphatic hydrocarbons having 1 to 10 C atoms,

The substituent R < ³ > is selected from the group comprising branched or unbranched fluorinated or non-fluorinated aliphatic hydrocarbons having 1 to 10 C atoms, aryl and heteroaryl, wherein a may be 0 or 1.

The inventors of the present invention have grasped that the bismuth complex having the above-mentioned ligand has particularly high heat resistance. Thus, the above-described complexes can be particularly well deposited by means of an evaporation source in which they collide with at least one wall of the walls of the evaporation source, and thus the method makes it possible to produce organic electronic devices with particularly low technological complexity, Do.

Another embodiment of the invention relates to a process according to the invention wherein the metal complex has a decomposition temperature above 10 K higher than the sublimation temperature of the metal complex and also above 20 K, especially above 40 K. A decomposition temperature higher than 70 K higher than the sublimation temperature of the metal complex is most preferred.

As the decomposition temperature far exceeds the sublimation temperature of the metal complex, the metal complex is more stable to collision with the wall of the evaporation source.

Another preferred embodiment of the present invention relates to a method according to the present invention wherein the matrix material of the organic electron layer deposited by simultaneous evaporation with, for example, a metal complex is, for example, one or more And is selected from the group consisting of or consisting of:

NPB (N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl)

(naphthalen-2-yl) -N, N'-bis (phenyl) -benzidine),

TPD (N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl)

Spiro TPD (N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl)

Spiro-NPB (N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl)

DMFL-TPD N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) -9,9-

N, N'-bis (phenyl) -2,2-dimethylbenzidine, N, N'-bis (naphthalen-

N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) -9,9-spirofluorene,

N, N'-bis (phenyl) -9,9-spirofluorene, N, N'-bis (naphthalen-

DMFL-NPB (N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -9,9-

DPFL-TPD (N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) -9,9-

DPFL-NPB (N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl)

Spiro-TAD (2,2 ', 7,7'-tetrakis (N, N-diphenylamino) -9,9'-spirobifluorene)

9,9-bis [4- (N, N-bis-biphenyl-4-yl-amino) phenyl] -9H-

N, N-bis-naphthalen-2-yl-amino) phenyl] -9H-fluorene,

N, N'-bis-phenyl-amino) -phenyl] -9H-fluorene, 9,9-bis [4- (N, N'-

N, N'-bis (phenyl) -benzidine, N, N'-bis (phenanthrene-

Bis [9,9-spiro-bifluoren-2-yl) -amino] -9,9-spiro-bifluorene,

2,2'-bis [N, N-bis (biphenyl-4-yl) amino] 9,9- spiro-

2,2'-bis (N, N-di-phenyl-amino) 9,9-spiro-

Di- [4- (N, N-ditolyl-amino) -phenyl] cyclohexane,

2,2 ', 7,7'-tetra (N, N-di-tolyl) amino-spiro-

N, N, N ', N'-tetra-naphthalen-2-yl-benzidine,

2,2 ', 7,7'-tetrakis [N-naphthalenyl (phenyl) -amino] -9,9-spirobifluorene,

Spiro-TTB (2,2 ', 7,7'-tetrakis- (N, N'-di-p-methylphenylamino) -9,9'-

Titanium oxide-phthalocyanine,

Copper-phthalocyanine,

2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane,

4,4 ', 4 "-tris (N-3-methylphenyl-N-phenyl-amino) triphenylamine,

4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenyl-amino) triphenylamine,

4,4 ', 4 "-tris (N- (1-naphthyl) -N-phenyl-amino) triphenylamine,

4,4 ', 4 "-tris (N, N-diphenyl-amino) triphenylamine,

Pyrazino [2,3-f] [1,10] phenanthroline-2,3-dicarbonitrile,

N, N, N ', N'-tetrakis (4-methoxyphenyl) benzidine.

This material was effectively used as an organic electronic device as a matrix material.

Another embodiment of the present invention relates to a method according to the invention, wherein one or more organic electronic layers of the organic electronic device to be produced by the method are electron blocking layers. Where simultaneous evaporation is performed using an evaporation source where a collision is made with at least one wall of the evaporation source, e.g., a linear evaporation source, at least partially with an electronically conductive matrix material.

Typical electronically conductive materials are:

2,2 ', 2 "- (1,3,5-benztriyl) tris (1-phenyl-1-H-benzimidazole)

2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole,

2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline,

8-hydroxyquinolinolato-lithium,

4- (naphthalen-1-yl) -3,5-diphenyl-4H-1,2,4-triazole,

1,3-bis [2- (2,2'-bipyridin-6-yl) -1,3,4-oxadiazo-5-yl] benzene,

4,7-diphenyl-1,10-phenanthroline,

3- (4-biphenylyl) -4-phenyl-5-tert-butylphenyl-1,2,4-triazole,

Bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum,

6,6'-bis [5- (biphenyl-4-yl) -1,3,4-oxadiazo-2-yl] -2,2'bipyridyl,

2-phenyl-9,10-di (naphthalen-2-yl) -anthracene,

Bis [2- (2,2'-bipyridin-6-yl) -1,3,4-oxadiazo-5-yl] -9,9-dimethylfluorene,

1,3-bis [2- (4-tert-butylphenyl) -1,3,4-oxadiazo-5-yl]

2- (naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline,

2,9-bis (naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline,

Tris (2,4,6-trimethyl-3- (pyridin-3-yl) phenyl)

1-Methyl-2- (4- (naphthalen-2-yl) phenyl) -1 H-imidazo [4,5-f] [1,10] phenanthroline.

The blocking and limitation of the electron flow is very important, for example, for high efficiency organic light emitting diodes (OLEDs), and therefore the method according to the invention is very useful in connection with industrial manufacture.

The invention relates to an organic electronic device comprising at least one organic electronic layer in addition to the method according to the invention. The organic electronic layer comprises a matrix, wherein the matrix comprises a bismuth complex as a dopant, for example as a p-type dopant. The bismuth complex comprises at least one ligand L bonded to a bismuth atom, wherein the ligands L may independently of one another have the general structure:

Here, one of the substituents R ¹ is 1 minute having one to ten C atoms is selected from branched or unbranched fluorinated group comprising aliphatic hydrocarbons, one of the substituents R ³ is minute having 10 C atoms branched or Non-branched fluorinated or non-fluorinated aliphatic hydrocarbons, aryl and heteroaryl, wherein a may be 0 or 1.

The inventors of the present invention have found that organic electronic devices of this type can be manufactured with much lower technical complexity than conventional organic electronic devices.

This is possible because the elements according to the invention comprise a bismuth complex of the type described above, which is characterized by a particularly high heat resistance. Thus, a manufacturing method requiring higher heat resistance of the metal complexes, that is, a production method in which collisions of complexes or complexes of complexes with at least one wall of the evaporation source occurs in an evaporation source for vapor deposition, is also possible. For example, it is possible to carry out the production by a linear evaporation source which requires particularly high thermal stability.

Another embodiment of the organic electronic device according to the present invention is characterized in that the ligand L is, independently,

≪ / RTI >

These devices are also particularly inexpensive besides particularly simple manufacture due to the heat resistance of the bismuth complex because the ligand is commercially available at a reasonable price and self-fabricating is unnecessary.

A particularly preferred embodiment of the organic electronic device according to the present invention relates to a device wherein the ligand L of the bismuth complex is substituted at positions 3 and 5 of the benzene ring. These complexes are particularly stable.

A particularly preferred embodiment of the organic electronic device according to the present invention relates to a device, wherein the ligand L of the bismuth complex is

이다.

to be.

A particularly preferred embodiment of the organic electronic device according to the present invention relates to a device, wherein the bismuth complex is a complex

이다.

to be.

The inventors of the present invention have found that such complexes exhibit excellent dopant characteristics and particularly high temperature stability. The complex is particularly stable at temperatures higher than the sublimation temperature by 70 < 0 > C and is therefore particularly suitable for production processes requiring high heat resistance of the dopants used. The complex is also well suited for vapor deposition in an evaporation source that requires specific stability of the complex, especially in an evaporation source where the complex impinges on at least one wall of the evaporation source. For example, the complexes can be laminated with the matrix material with low complexity with respect to deposition by a linear evaporation source.

For this reason, the organic electronic devices including the complexes can be manufactured particularly simply and inexpensively on an industrial basis, and at the same time include an organic electronic layer having excellent electrical properties, for example, in terms of conductivity.

The selection criteria disclosed in the application fields can be applied without limitation because the size, design, material selection, and exceptional conditions unique to the technical concept of the devices to be used according to the invention described in the above-mentioned, claimed and embodiments are not relevant.

Other details, features and advantages of the subject matter of the present invention are set forth in the following description of the drawings, related embodiments and reference examples.

Fig. 1 schematically shows the configuration of the organic light emitting diode 10. The light emitting diode may include a glass layer 1, a transparent conductive oxide (TCO) or a PEDOT: PPS or PANI layer 2, a hole injection layer 3, a hole transport layer (HTL) 4, an emitter layer (EML) (HBL) 6, an electron transport layer (ETL) 7, an electron injection layer 8, and a cathode layer 9.
Fig. 2 schematically shows the structure of an organic solar cell having a PIN-structure 20 for converting light 21 into electric current. The solar cell comprises a layer of indium-tin-oxide 22; a p-type doping layer 23; An absorbent layer 24; an n-type doping layer 25 and a metal layer 26.
Fig. 3 schematically shows a possible cross-section of the organic field effect transistor 30. Fig. A gate electrode 32, a gate dielectric 33, an evaporation source and a drain contact 34 + 35, and an organic semiconductor 36 are stacked on the substrate 31. The hatched locations indicate locations where contact doping is useful.
Fig. 4 shows the constitution of the prior art according to the point vapor source of Greaphys. The point vapor source includes a crucible (41). The material to be deposited is evaporated in a vacuum crucible. After evaporation of the material, the molecules leave the point vapor source through the discharge opening 42. For example, molecules of a metal complex acting as a dopant due to a high average free path in a vacuum (10 ^-5 to 10 ^-6 mbar) reach the substrate without further collision. This means that the material must be thermally stable above the sublimation temperature to allow it to be deposited on the substrate without degradation. In particular, the dopant deposited by the point vapor source can be deposited directly on the substrate to be coated by being placed directly in the opening of the evaporation source, rather than reaching the wall of the evaporation source. The area of the porcelain where the dopant is evaporated, the discharge opening and the substrate are arranged in a straight line. In particular, the dopant can be deposited without being bypassed by a line system or a spray system before the dopant reaches the substrate.
Figure 5 illustrates the configuration of a linear deposition source, illustratively, in a linear deposition source as schematically illustrated by Vecco. The linear evaporation source includes a crucible 51 that can be removed. After evaporation of the material to be deposited in the crucible, for example a dopant, the dopant in the gaseous state is guided through the line 53 towards the discharge opening 52. The discharge opening 52 may be, for example, in the form of a gap or may be a hole train. The linear deposition source does not allow direct linear access to the substrate in the dopant, and the dopant is rather deflected primarily in the linear deposition source. Here, a plurality of collisions of the dopant with the wall of the linear evaporation source are made. The linear deposition source may also include a controllable valve 54, a flow regulator 56 and suitable wiring 55 for an electronic control of, for example, a heating device or valve. A large area of deposition can be achieved particularly well by the desired guide of gas flow.
Figure 6 shows the current density versus voltage for an undoped matrix material and a doped matrix material as Example I; As the matrix material, a hole conductor, 2,2'7,7'-tetra (N, N-ditolyl) amino-9,9-spiro-bifluorene, abbreviated as Spiro-TTB was used. The current density-voltage characteristic curve demonstrates the sufficient doping characteristics of 15% Cu (3,5-tfmb) in the hole conductor spiro -TTB.
Figure 7 shows current density versus voltage and current density versus external field strength for Example II for 1-TNata doped with bismuth (III) tris-3,5-trifluoromethyl-benzoate do. In order to enable comparison of the electrical characteristics under the same conditions as the comparative example, the measurement was carried out on the doped matrix material formed by the point vapor source. Measurements were made at three different dopant contents, respectively. The voltage characteristic curves show good conductivity and demonstrate excellent dopant concentrations of bismuth (III) tris-3,5-trifluoromethyl-benzoate.
Figure 8 shows the current density versus voltage for a current density versus voltage with respect to Example II for the matrix material 1-TNata, Spiro-TTB and alpha -NPB doped with bismuth (III) tris-3,5-trifluoromethyl- And the current density with respect to the external electric field intensity.
9 is a graph illustrating the effect of voltage (V) on the doping matrix material obtained by deposition by a point vapor source, with reference to Reference Example I for 1-TNata doped with bismuth (III) tris (2,6- difluorobenzoate) ≪ / RTI > and the current density for the external field strength. The measurements were each carried out at three different dopant contents.
Figure 10 shows the current density versus voltage for a reference material I with respect to matrix material 1-TNata doped with bismuth (III) tris (2,6-difluorobenzoate), Spiro -TTB and a- And the current density with respect to the external electric field intensity.
11 is a graph showing the current versus voltage for a doped matrix material obtained by deposition by a point vapor source, with reference to Reference Example II for 1-TNata doped with bismuth (III) tris (4-fluorobenzoate) Density and current density versus external field strength. Measurements were made at three different dopant contents, respectively.
Figure 12 shows current density versus external field strength for voltage < RTI ID = 0.0 > (I) < / RTI > with respect to Reference Example II for matrix material 1-TNata, Spiro -TTB and alpha -NPB doped with bismuth (III) tris (4-fluorobenzoate) ≪ / RTI >
Figure 13 is a graph of the current versus voltage for a doped matrix material obtained by deposition by a point vapor source in reference to Reference Example III for 1-TNata doped with bismuth (III) tris (3-fluorobenzoate) Density and current density versus external field strength. Measurements were made at three different dopant contents, respectively.
Figure 14 shows the current density and external field strength for voltage with respect to Reference Example III for the matrix material 1-TNata, Spiro-TTB and alpha -NPB doped with bismuth (III) tris (3-fluorobenzoate) ≪ / RTI >
15 is a graph showing the relationship between voltage (V) in the case of doped matrix material obtained by deposition by a point vapor source in reference to Reference Example IV for 1-TNata doped with bismuth (III) tris (3,5-difluorobenzoate) ≪ / RTI > and the current density for the external field strength. Measurements were made at three different dopant contents, respectively.
Figure 16 shows the current density versus voltage for a reference material IV with respect to matrix material 1-TNata doped with bismuth (III) tris (3,5-difluorobenzoate), Spiro -TTB and a- And the current density with respect to the external electric field intensity.
FIG. 17 is a graph of the relative dielectric constants of a doped matrix material obtained by deposition by a point vapor source in reference to Reference Example V for 1-TNata doped with bismuth (III) tris (3,4,5-trifluorobenzoate) The current density versus voltage and the current density versus external field strength. Measurements were made at three different dopant contents, respectively.
Figure 18 shows the current density versus voltage for a reference material V of the matrix material 1-TNata, Spiro-TTB and alpha -NPB doped with bismuth (III) tris (3,4,5- trifluorobenzoate) And the current density with respect to the external electric field intensity.
Figure 19 is a graph of the current density versus voltage for a doped matrix material obtained by deposition by a point vapor source in reference to Reference Example VI for 1-TNata doped with bismuth (III) tris (perfluorobenzoate) And the current density with respect to the external electric field intensity. Measurements were made at three different dopant contents, respectively.
20 is a graph showing the relationship between the current density versus voltage and the external field strength on voltage with respect to Reference Example VI for matrix material 1-TNata, Spiro-TTB and alpha -NPB doped with bismuth (III) tris (perfluorobenzoate) ≪ / RTI >
Figure 21 is a graph of the relative dielectric constants for voltage for a doped matrix material obtained by deposition by a point vapor source in reference to Example VII for 1-TNata doped with bismuth (III) tris (4-perfluorotoluate) Current density versus current density versus external field strength. Measurements were made at three different dopant contents, respectively.
22 is a graph showing the relationship between the current density versus voltage and the external field (voltage) for voltage < RTI ID = 0.0 > (I) < / RTI > with respect to Reference Example VII for matrix material 1-TNata, Spiro- Current density versus intensity.
Figure 23 is a graph of the current density versus voltage for a doped matrix material obtained by deposition by a point vapor source with respect to Reference Example VIII for 1-TNata doped with bismuth (III) tris (trifluoroacetate) And the current density with respect to the external electric field intensity. Measurements were made at three different dopant contents, respectively.
24 is a graph showing the relationship between the current density versus voltage and the external field strength versus voltage for the reference material VIII doped with bismuth (III) tris (trifluoroacetate) 1-TNata, Spiro -TTB and alpha -NPB Current density.
25 is a graph comparing the current density versus voltage for a doped matrix material obtained by deposition by a point vapor source and the external current density versus current for a doped < RTI ID = 0.0 > And current density with respect to electric field intensity. Measurements were made at three different dopant contents, respectively.
Figure 26 shows current density versus current density versus external field strength versus voltage with respect to Reference Example IX for matrix materials 1-TNata, Spiro -TTB, and [alpha] -NPB doped with bismuth (III) tris (triacetate) / RTI >

Two examples I and II will be described below. The two metal complexes Cu (I) bis-trifluoromethylbenzoate (Example I) and bismuth (III) tris-3,5-trifluoromethylbenzoate (Example II) It has a significantly higher decomposition temperature and is very thermally stable. The two complexes can be deposited by an evaporation source, where the complexes collide with at least one wall of the evaporation source. For example, the two complexes have sufficiently high stability for vapor deposition by a linear deposition source. This was experimentally demonstrated by so-called ampoule testing.

All other reference examples, REFERENCE EXAMPLES I-IX, did not show sufficient stability in an ampule test. The inventors have experimentally found that these components are not suitable for deposition by an evaporation source in which the complex impinges.

The electrical properties of each doped layer were also investigated. Since the metal complexes of Reference Examples I to IX are not sufficiently stable for deposition by at least one wall of the deposition source and the deposition source by which the complex impinges, measurements are made on the organic electron layer deposited by the point vapor source Respectively. For example, the complexes of Reference Examples I to IX are not stable enough for deposition by a linear deposition source.

Example I

Example I relates to the metal complex Cu (I) bis-trifluoromethyl benzoate (hereinafter simply referred to as Cu (3,5-tfmb)).

Generally, a plurality of Cu (I) complexes of the fluorinated derivatives of benzoates can be prepared in the following manner.

In a similar manner, a number of metal complexes used in the process according to the invention can be prepared.

Thus, for example, the metal complex 3,5-bis- (trifluoromethyl-benzoate) of Cu (I) trifluoroacetate can be obtained in accordance with the following rules.

5 g (7.08 mmol) of Cu (I) trifluoroacetate was added to 7.5 g (29.03 mmol) of 3,5-bis- (trifluoromethylbenzoic acid) in a 250 ml two- In a glove box) weighing. The mixture is mixed with 80 ml of toluene and 70 ml of benzene, at which time a green reaction liquid is formed. The reaction solution is heated to weak reflux (bath temperature about 90 ° C.) and the solvent is distilled as a result. The cream-gray product is left, and the product is dried in vacuo. The yield after one sublimation is 6.98 g (76%). The sublimation range of the components is from 160 to 180 ° C at 2 x 10 ^-5 mbar.

By the ampoule test, Cu (3,5-tfmb) could be proved stable to at least 225 ° C.

For the test ampoules, it melts to about 100 to 500 mg ingredient to be tested in a base pressure of 10 ^-5 to 10 ^-6 mbar. The ampoule is then heated in an oven and left at each temperature for about 100 hours. By optical inspection, it can be determined whether or not the decomposition of the metal complex has been carried out, since the decomposition causes discoloration, mainly browning. The ampoule is finally further heated at the first test temperature in the 10 to 20 K step after about 100 hours and left in the oven for about 100 hours at the new test temperature. The experiment continues until the discoloration finally shows decomposition.

In control experiments, further ampoules containing fresh samples of the same metal complex to be tested after each optical determination are again heated in the oven for approximately 100 hours. Where the heating is at a temperature slightly below the optically determined decomposition temperature. The sample thus treated is then examined by elemental analysis and the stability of the complex is demonstrated by elemental composition.

For the Cu (I) bis-trifluoromethylbenzoate according to Example I, the ampoule test was conducted at three different temperatures: 210 ° C, 230 ° C, 240 ° C.

The measurement demonstrates that the complex is stable up to at least 225 ° C. This was demonstrated by elemental analysis.

Therefore, Cu (3,5-tfmb) is suitable for vapor deposition by a vapor source by means of an evaporation source in which a complex collides with at least one wall of the evaporation source walls. For example, vapor deposition by a linear deposition source.

The layer doped with Cu (3,5-tfmb) has very good optical transmittance in the visible range. Cu (3,5-tfmb) is also characterized by a sufficiently high dopant concentration.

In addition, as shown by FIG. 6, the organic layer doped with Cu (3,5-tfmb) has excellent conductivity.

Example II

Example II relates to the process according to the invention, wherein the metal complex is bismuth (III) tris-3,5-trifluoromethylbenzoate (hereinafter simply referred to as the ratio (3,5-tfmb) ₃ ).

The bismuth complexes according to Example II and the metal complexes of Reference Examples I to VII described below were prepared according to the general method according to Scheme 1 below:

Scheme 1:

In the case of the ratio (3,5-tfmb) ₃ , the residues R ^B and R ^D , i.e. the residues at the 3,5-position are each a CF ₃ substituent, and the residues R ^A , R ^C and R ^E are each a hydrogen atom.

The yield of the ratio (3,5-tfmb) ₃ after purification by sublimation was verified by elemental analysis (measured value: 33.5% carbon; 0.5% hydrogen; calculated value: 33.06% carbon, 0.92% hydrogen).

The thermal stability of bismuth (III) tris-3,5-trifluoromethylbenzoate was determined by an ampule test as described above in connection with Example I. Therefore, the metal complex is stable even at heat treatment at 330 ° C for 144 hours. No discoloration of the ampoule is observed at temperatures below 330 ° C. A slight discoloration occurs only at 330 ° C. The elemental analysis data also demonstrate that the complex is thermally stable up to 330 ° C in the statistical error range.

Similar tests were also conducted for 144 hours at 260 ° C, 280 ° C, 315 ° C, and 330 ° C, respectively, as shown in Table 1. Samples of the temperature treated components were each examined using elemental analysis, where the carbon content was determined. Based on the deviation of the carbon content thus determined from the predicted carbon content of the undecomposable complex, it is possible to make inferences about the resolution of the complex after each heat treatment. Bismuth (III) tris-3,5-trifluoromethylbenzoate according to Example II, by a series of tests, has particularly high thermal stability, and at a temperature above 330 ° C It could be proved that decomposition occurred.

Table 1: Determination of carbon content by elemental analysis at two different positions (position A, position B) of the ampoule in which each component is deposited according to the ampoule test.

Small deviations of the theoretically calculated content (33.06%) and the carbon content determined at temperatures below 330 ° C demonstrate the high thermal stability of bismuth (III) tris-3,5-trifluoromethylbenzoate. Certain decomposition of the complex is observed only at temperatures above 330 ° C.

Thus, the elemental analysis demonstrates the stability of the complex under statistical errors at temperatures below 330 ° C.

Thus, because of their high thermal stability, dopants comprising fluorinated alkyl substituents R < ¹ >, as can be seen in the example of bismuth (III) tris-3,5-trifluoromethylbenzoate, And the metal complex, i. E. The dopant, in the evaporation source collides with at least one wall of the evaporation source. For example, the metal complex is stable enough to allow it to be deposited from the vapor phase by a linear deposition source without decomposition.

The layer doped with the ratio (3,5-tfmb) ₃ has a very good optical transmittance in the visible range.

The ratio (3,5-tfmb) ₃ is also characterized by a sufficiently good dopant concentration. This is further illustrated by the experimental data summarized below.

Electrical properties of doped organic layer in a non-(3,5-tfmb) ₃ is 7, are summarized in Figure 8 and Table 2, Table 3.

Table 2: Summary of electrical properties of 1-TNata doped with non (3,5-tfmb) ₃ . The electrical properties of the matrix, especially at three different dopant contents (1: 8, 1: 4 and 1: 2)

The electrical properties specified in Table 2 and all other tables for various materials were determined by measurement in a 200 nm thick organic layer supported on an ITO (indium-tin-oxide) substrate, which was deposited by simultaneous evaporation Lt; / RTI >

Here, the experimental molar ratio represents the molar ratio of the matrix material to the metal complex, respectively. ₀ represents the conductivity of the measured organic electronic layer. ρ _{c .; 0} represents contact resistance. E _bi represents the electric field intensity of the internal field of the semiconductor material (referred to as "built-in electric field" in English), which is obtained from the deviation of the work function between the anode and the cathode of the organic electronic device. ε _r is the dielectric constant of the material obtained by simultaneous evaporation.

A series of other parameters have been determined in relation to the transport regime of the charge carriers in the organic electronic layer as described in the various conductive theories of the literature. Here r represents the empirical factor (called the "trap distribution factor" in English), which means the exponential distribution according to the charge carrier-transport model (Steiger et al., "Energetic trap distributions in organic semiconductors", Synthetic Metals 2002, 129 1), 1-7; Schwoerer et al., "Organic Molecular Soldis" Wiley-VCH, 2007). μ ₀ is the charge carrier mobility, and γ represents the field activation factor (referred to in English as "field-activation factor"). γ is important in relation to the description of charge transport according to the Murgatroyd equation: Murgatroyd, PN "Theory of space-charge-limited current enhancement by Frenkel effect" Journal of Physics D: Applied Physics 1979, 3 (2), 151.

Here, the terms "too conductive", "ballistic", "no ohmic contact", "trapping", "aging", "no TFLC", "Compliance" used in Tables 2-31 have the following meanings: too conductive "indicates that measurement is meaningless due to too high a conductivity of the layer. The term "no ohmic contact" means that no electrical contact was present. The term "Compliance" indicates that the preset current limit of the measuring device has not been reached. The term "TFLC" means "trap-filled limited regime " according to the teachings of Steiger et al. And Schwoerer et al. And refers to a transport regime for the charge carrier of the organic electronic layer. The terms "ballistic", "trapping" and "aging" refer to "ballistic", "trapping" and "aging". The terms " ballistic ", "trapping ", and" aging " relate to other transport regimes in accordance with the different conductivity models described in the literature. Where the different conductivity regimes can be grasped in the index of the current-voltage dependency.

Each abbreviation also applies to Tables 3 to 21 in a similar manner.

Table 3 (1: 2) ratio (3,5-tfmb) doped matrix material in _three 1-TNata, α-NPB, and the summation of the electrical properties of the spiro -TTB. The electrical properties of doping various matrix materials are compared.

The measurements were carried out using a ratio (3,5-tfmb) ₃ Demonstrate that the doped matrix material has excellent electrical properties, particularly sufficiently good conductivity.

Which subsequently did not exhibit sufficient heat resistance in each of the ampoule tests, unlike Cu (3,5-tfmb) according to Example I and the ratio (3,5-tfmb) ₃ according to Example II, And by comparison with the electrical properties of a number of other complexes which are not suitable for deposition into vapor phase by evaporation source in which collision occurs.

Reference Example I

Reference Example I relates to the use of bismuth (III) tris (2,6-difluorobenzoate), simply non (2,6-dfb) ₃ , as a metal complex for vapor deposition.

The synthesis of the ratio (2,6-dfb) ₃ was carried out according to Scheme 1. For the ratio (2,6-dfb) ₃ , in the scheme 1, the residues R ^A and R ^E are each a fluorine atom, and the remaining substituents R ^B , R ^C and R ^D are each a hydrogen atom.

The yield of the ratio (2,6-dfb) ₃ was demonstrated by elemental analysis after purification by sublimation (measured value: 36.2% carbon; 1.5% hydrogen; calculated value: 37.06% carbon; 1.32% hydrogen).

The electrical properties of the organic layer doped with the non (2,6-dfb) ₃ are summarized in FIG. 9, FIG. 10 and Table 4,

Table 4: Summary of electrical properties of 1-TNata doped with non (2,6-dfb) ₃ .

Table 5: Summary of the electrical properties of 1-TNata, alpha -NPB and Spiro -TTB doped matrix materials with (1: 2) ratio (2,6-dfb) ₃ .

Reference Example II

Reference Example II relates to the use of bismuth (III) tris (4-fluorobenzoate), simply non (4-fb) ₃ as the metal complex for vapor deposition.

The synthesis of the ratio (4-fb) ₃ was carried out according to Scheme 1. In the case of the ratio (4-fb) ₃ , the residues R ^A , R ^B , R ^D, and R ^E in Scheme 1 are hydrogen atoms and only R ^C is a fluorine atom.

The yield of the ratio (4-fb) ₃ was confirmed by elemental analysis after purification by sublimation (measured value: 42.4% of carbon; 2.3% of hydrogen; calculated value: 40.26% of carbon; 1.92% of hydrogen).

Electrical characteristics of the organic layer doped with the non-(4-fb) ₃ are summarized in FIG. 11, FIG. 12, and Table 6,

Table 6: Summary of electrical properties of 1-TNata doped with non (4-fb) ₃ .

Table 7: (1: 2) ratio (4-fb) doped matrix material in _three 1-TNata, α-NPB, and the summation of the electrical properties of the spiro -TTB.

Reference Example III

Reference Example III relates to the use of bismuth (III) tris (3-fluorobenzoate), simply non (3-fb) ₃ as a metal complex for vapor deposition.

The synthesis of the ratio (3-fb) ₃ was carried out according to Scheme 1. In the case of the ratio (3-fb) ₃ , the residues R ^A , R ^C , R ^D and R ^E in the reaction scheme 1 are hydrogen atoms and only R ^C is a fluorine atom.

The yield of the ratio (3-fb) ₃ was confirmed by elemental analysis after purification by sublimation (measured value: 39.2% of carbon; 2.3% of hydrogen; calculated value: 40.26% of carbon; 1.92% of hydrogen).

The electrical characteristics of the organic layer doped with non-3-fb ₃ are summarized in FIG. 13, FIG. 14, and Table 8,

Table 8: Summary of Electrical Properties of 1-TNata Doped with Non (3-fb) ₃ .

Table 9: (1: 2) ratio (3-fb) doped matrix material in _three 1-TNata, α-NPB, and the summation of the electrical properties of the spiro -TTB.

Reference Example IV

Reference Example IV relates to the use of bismuth (III) tris (3,5-difluorobenzoate), simply non (3,5-dfb) ₃ , as a metal complex for vapor deposition.

Synthesis of the ratio (3,5-dfb) ₃ was carried out according to Scheme 1. In the case of the ratio (3,5-dfb) ₃ , the residues R ^A , R ^C, and R ^E in the reaction scheme 1 are each a hydrogen atom, and R ^B and R ^D are each a fluorine atom.

The yield of the ratio (3,5-dfb) ₃ was confirmed by elemental analysis after purification by sublimation (measured value: 36.3% carbon; 1.4% hydrogen; calculated value: 37.06% carbon;

The electrical characteristics of the organic layer doped with the non-doped (3,5-dfb) ₃ are summarized in FIG. 15, FIG. 16, and Table 10,

Table 10: Summary of electrical properties of 1-TNata doped with non (3,5-dfb) ₃ .

Table 11: Summary of the electrical properties of 1-TNata, α-NPB and Spiro-TTB doped matrix materials with (1: 2) ratio (3,5-dfb) ₃ .

Reference Example V

Reference Example V relates to the use of bismuth (III) tris (3,4,5-trifluorobenzoate) as a metal complex for vapor deposition, simply the ratio (3,4,5-tfb) ₃ .

The synthesis of the ratio (3,4,5-dfb) ₃ was carried out according to Scheme 1. In the case of the ratio (3,4,5-tfb) ₃ , in the scheme 1, the residues R ^A and R ^E are each a hydrogen atom and the remaining substituents R ^B and R ^C And R ^D are each a fluorine atom.

The yield of the ratio (3,4,5-tfb) ₃ was verified by elemental analysis after purification by sublimation (measured value: 33.8% of carbon; 1.2% of hydrogen; calculated value: 34.33% of carbon; 0.82% of hydrogen).

The electrical characteristics of the organic layer doped with the ratio (3,4,5-tfb) ₃ are summarized in FIG. 17, FIG. 18, and Table 12,

Table 12: Summary of electrical properties of 1-TNata doped with non (3,4,5-tfb) ₃ .

Table 13: (1: 2) ratio (3,4,5-tfb) doped matrix material in _three 1-TNata, α-NPB, and the summation of the electrical properties of the spiro -TTB.

Reference Example VI

Reference Example VI relates to the use of bismuth (III) tris (perfluorobenzoate), simply non (pfb) ₃ , as a metal complex for vapor deposition.

The synthesis of the ratio (pfb) ₃ was carried out according to Scheme 1. In the case of the ratio (pfb) ₃ , all five residues R ^A to R ^E in Scheme 1 are each a fluorine atom.

The yield of the ratio (pfb) ₃ was confirmed by elemental analysis after purification by sublimation (measured value: 29.9 (6)% of carbon; calculated value: 29.93% of carbon).

The electrical characteristics of the organic layer doped with the ratio (pfb) ₃ are summarized in FIG. 19, FIG. 20, and Table 14, and Table 15.

Table 14: Summary of electrical properties of 1-TNata doped with non (pfb) ₃ .

Table 15: Summary of the electrical properties of 1-TNata, alpha -NPB and Spiro -TTB doped matrix materials with (1: 2) ratio (pfb) ₃ .

Reference Example VII

Reference Example VII relates to the use of bismuth (III) tris (4-perfluorotoluate), simply as 4-pftl ₃ , as a metal complex for vapor deposition.

In the case of the ratio (4-pftl) ₃ , the residues R ^A , R ^B , R ^D and R ^E in the scheme 1 are each a fluorine atom and R ^C is a CF ₃ - group.

The yield of non (4-pftl) ₃ was demonstrated by elemental analysis after purification by sublimation (measured value: 30.0% of carbon; calculated value: 29.03% of carbon).

The electrical properties of the organic layer doped with non (4-pftl) ₃ are summarized in Figures 21, 22 and Table 16,

Table 16: Summary of electrical properties of 1-TNata doped with non (4-pftl) ₃ .

Table 17: (1: 2) ratio (4-pftl) doped matrix material in _three 1-TNata, α-NPB, and the summation of the electrical properties of the spiro -TTB.

Other conventional metal complexes, including acetate-based and trifluoroacetate-based ligands, have also been used by the inventors for comparison with the complexes used in the process according to the invention:

Reference Example VIII

Reference Example VIII relates to the use of bismuth (III) tris (trifluoroacetate), simply as tfa ₃ , as the metal complex for vapor deposition. The preparation is described in the literature (see, for example, Suzuki, H., Matano, Y. Organobismut Chemistry, Elsevier 2001).

The electrical properties of the organic layer doped with the ratio (tfa) ₃ are summarized in Figures 23, 24 and Table 18,

Table 18: Summary of electrical properties of 1-TNata doped with non-tfa ₃ .

"After TFLC, the slope decreases to a limit near 3/2 (ballistic) (after TFLC, the slope decreases to near 3/2 (ballistic))" and "Just before exponentially increasing (aging) (Aging) ") refers to the transition from the charge transport regime to the other regime.

Table 19: Summary of the electrical properties of 1-TNata, alpha -NPB and Spiro -TTB doped matrix materials with (1: 2) ratio (tfa) ₃ .

From the data it can be seen that the complex doped with the non-fluorinated ligand is not much better than the complex doped with the fluorinated ligand. These complexes are also not suitable for evaporation sources in which collision with at least one wall of the evaporation source occurs, as in other reference examples.

Reference Example I X

Reference Example IX relates to the use of bismuth (III) tris (triacetate), simply non (ac) ₃ , as a metal complex for vapor deposition. The complexes are commercially available.

The electrical properties of the organic layer doped with non (ac) ₃ are summarized in FIG. 25, FIG. 26, and Table 20, Table 21.

Table 20: Summary of electrical properties of 1-TNata doped with non (ac) ₃ .

Table 21: Summary of the electrical properties of 1-TNata, alpha -NPB and Spiro -TTB doped matrix materials with (1: 2) non (ac) ₃ .

Many of the foregoing Examples, Example I, Example II, and most of the Reference Examples have a sufficient dopant concentration. The matrix material doped with such complexes exhibits sufficiently good conductivity in the case of Examples I and II and in many reference examples.

Metal complexes of Example I and Example II with respect to complex stability, particularly thermal stability, meet the demanding requirements for deposition using an evaporation source in which a complex collides with at least one wall of the evaporation source. Alternatively, none of the complexes of the complexes of the reference examples exhibited sufficient stability to be vapor-deposited using vapor sources that collide with the walls of the vapor source.

For example, only the complexes of Example I and Example II can be deposited using a linear evaporation source, and the complexes of the reference example can not be deposited. Although all complexes are sufficiently stable for deposition using a point vapor source, only complexes containing at least one substituent R < ¹ > meet high stability requirements.

The individual combinations of elements and features of the above-described implementations are exemplary; It is expressly contemplated that alternatives and alternatives to the teachings contained in this document, as well as those cited in the present teachings, are contemplated. Those skilled in the art will appreciate that variations, modifications and other implementations described herein can be made without departing from the spirit of the invention and the scope of the invention.

Therefore, the above description is illustrative and should not be construed as limiting. The word "comprising" used in the claims does not exclude other elements or steps. The indefinite article "one" does not exclude plural meanings. The mere fact that certain means are recited in different claims does not mean that a combination of the means can not be used advantageously. The scope of the present invention is defined by the following claims and their equivalents.

This patent application claims priority from German Patent Application 102014114231.4, the disclosure of which is incorporated herein by reference.

Claims (15)

A method of manufacturing an organic electronic device, the device comprising at least one organic electronic layer having a matrix, the matrix comprising a metal complex as a dopant, the metal complex comprising at least one metal atom M and at least one metal atom Wherein the ligand L comprises at least one ligand L independently of one another and has the structure: wherein the deposition of the dopant of the at least one organic electronic layer is performed by vapor deposition using an evaporation source, And is configured to collide with at least one wall of the evaporation source.

In the above formula, E ¹ and E ² independently of one another can be oxygen, sulfur, selenium, NH or NR ', wherein R' is selected from the group comprising alkyl or aryl and is bonded to the substituted benzene ring of ligand L ;
The substituent R &^lt; 1 > is independently selected from the group comprising branched or unbranched fluorinated aliphatic hydrocarbons having 1 to 10 C atoms, where n is 1 to 5;
Substituent R ² is independently from each other selected from the group comprising -CN, a branched or unbranched aliphatic hydrocarbon having 1 to 10 C atoms, aryl and heteroaryl, wherein m is from 0 to a maximum of 5-n. The method according to claim 1, wherein the vapor deposition is performed using a linear evaporation source. 3. The method according to claim 1 or 2, wherein the metal M of the metal complex is selected from the group consisting of a rare earth metal of Groups 13 to 15 of the periodic table and metals Cu, Cr, Mo, Rh and Ru. 4. The method according to any one of claims 1 to 3, wherein the metal M of the metal complex is Bi or Cu. To claim 1, wherein A method according to any one of claim 4, wherein at least one of the substituents R ¹ is -CF ₃ group method. Any one of claims 1 to A method according to any one of claim 5, wherein the ligand L is a method to form accurately the two have a substituent R ^1, the substituent groups each -CF _3. The method according to any one of claims 1 to 6 wherein the ligand L is exactly have the two substituents R ^1, the substituent is disposed on each benzene ring in 3,5-position to form a group -CF _3, and ligand L Lt; / RTI > 8. Compounds according to any one of claims 1 to 7, wherein the substituents R < ² > are independently from each other methyl-, ethyl-, n-propyl-, iso-propyl-, n-butyl-, isobutyl-, - and substituted or unsubstituted phenyl-. Any one of claims 1 to A method according to any one of items 8, E ¹ and E ² are both a method of producing oxygen. 10. A compound according to any one of claims 1 to 9, wherein the ligand L is independently

≪ / RTI > 11. The metal complex according to any one of claims 1 to 10, wherein the metal complex is a bismuth complex, L may have the following general formula:

In the above formula, substituent R &^lt; 1 > is selected from the group comprising branched or unbranched fluorinated aliphatic hydrocarbons having 1 to 10 C atoms,
Wherein the substituent R < ³ > is selected from the group consisting of branched or unbranched fluorinated or non-fluorinated aliphatic hydrocarbons having 1 to 10 C atoms, aryl and heteroaryl. 12. The metal complex according to any one of claims 1 to 11, wherein the metal complex has a decomposition temperature higher than 10 K (Kelvin), especially more than 40 K, most preferably more than 70 K higher than the sublimation temperature of the metal complex Way. An organic electronic device comprising at least one organic electronic layer, the organic electronic layer comprising a matrix, the matrix comprising a bismuth complex as a dopant, the bismuth complex comprising at least one ligand L bonded to a bismuth atom , And the ligand L can independently have the following general structural formula:

In the above formula, substituent R &^lt; 1 > is selected from the group comprising branched or unbranched fluorinated aliphatic hydrocarbons having 1 to 10 C atoms,
Substituent R < ³ > is selected from the group comprising branched or unbranched fluorinated or non-fluorinated aliphatic hydrocarbons having 1 to 10 C atoms, aryl and heteroaryl, wherein a may be 0 or 1. 14. The compound of claim 13, wherein L is independently

≪ / RTI > 15. The bismuth complex according to claim 13 or 14, wherein the bismuth complex has the following complex:

Organic electronic device.

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